Crashes between cars and trains at rail level crossings are problematic worldwide. Despite this, key facets of driver behaviour at rail level crossings, such as situation awareness and decision making, remain ambiguous. This is largely down to the inability of existing methodologies to describe or evaluate the cognitive aspects of driver behaviour when negotiating rail level crossings. This paper showcases an on-road approach for examining driver situation awareness at rail level crossings. The study presented involved participants, classified either as novice or experienced drivers, providing concurrent verbal protocols as they drove a pre-determined urban route incorporating four rail level crossings. Driver situation awareness was modelled using a network analysis-based approach and the structure and content of the networks was assessed. The analysis revealed key differences between novice and experienced drivers situation awareness at rail level crossings. In closing, the benefits of the on-road approach are discussed and a series of wider driver behaviour applications are proposed.